Antiknock compound and motor fuel containing same



Patented July 4, 1944 UNITED STATES 7 2.35am V aN'nKNocx comrounn ANDMoron FUEL con'mmmo seam Richmond 'r. Bell, peel-nerd, m, aesignor toThe Pure Oil Company, Chicago, 111., a corporation of Ohio 'No Drawing.Application October 15, 1941 SerialNo. 415,066

18 Claims. (01. 44-88) This invention relates to high octane motor Ifuel, to a method of preparing the s ame, and to a new composition ofmatter having the ability to increase octane number of hydrocarbon motorfuel.

Although it is known that various metal carbonyls and carbonyl compoundssuch as iron pentacarbonyl, iron tetracarbonyl, nitrosyl carbonyls ofvarious metals and metal tricarbonyl mercaptides will impart improvedantiknock properties to hydrocarbon motor. fuels, these compounds allhave a serious drawback in that.

they are relatively unstable in the presence of light and/or air atordinary atmospheric tembility under normal storage conditions, in aseries of storage tests run on motor fuel samples the octane of whichhad been improved by the addition of iron tricarbonyl mercaptides, itwas found that after 56 days in storage in the presence of light and airat room temperature, not only was a large amount of fiocculentprecipitate formed, but from 50% to 100% of the octane increase causedby the addition of the iron com,- pound had been lost.

The object of this invention is to provide a carbonyl compound which hasa high degree of stability in the presence of light and/or air.

Another object of this invention is to provide rating of the motor fueland the motor fuel will remain stable over long periods of time withoutformation of precipitatesand without deterioration in octane rating.

In order to prepare the novel compositions in accordance with myinvention, the polymeric metal carbonyl-for example, irontetracarbonyl-is added to an oxygen-free solution of lecithin or otherphosphatide iii a hydrocarbon solvent such as naphtha, or other inertsolvent, and the mixture agitated or stirred at a temperature ofapproximately 170-180" F. in the absence of oxygen for a period ofthirty to sixty minutes. A complete color change takes place from darkgreen to dark yellow or deep red, depending upon the concentration ofthe solution, indicating that a reaction takes place.

In preparing the reaction product between the carbonyl and thephosphatide the ratio of carbonyl to phosphatide may vary within ratherwide limits. I have found that a mole ratio of polymeric metal carbonylto phosphatide ranging from 1 to 1, to a ratio of 10 to 1 to besatisfactory.

A series of blends of rrotor fuel were made up from straight run naphthaand various amounts of iron pentacarbonyl, iron tetracarbonyl and thereaction product of iron tetracarbonyl and lecithin, the reactionproduct being designated in the following table as Fe X, and theincreased octane obtained in each case was determined. The results aretabulated in Table I:

Table I Oct. No. increase calcu- Oct Octane lated in di- Semple NaphtbaN Compound present Iron Lecithin No.inrect procrease portion for l g.iron per gel.

1 Blend "A" 2 Blend .B

as lecithin and cephalin are reacted with polymeric metal carbonyls suchas' iron tetracarbonyl, iron nonacarbonyl, cobalt tetracarbonyl andcobalt tricarbonyl, a reaction product is formed which is highly stableto light and/or air and which when added to hydrocarbon motor fuel inrelatively small amounts increases the octane so In the case of thenaphthas containing the 50 iron pentacarbonyl andthe iron tetracarbonyl,

the solutions were made by dissolving these two iron compoundsin naphthacontaining lecithin in the amount indicated in the table. In the case ofthe Fe X reaction product, it was dis- 55 solved in naphtha which didnot contain lecithin,

but the table indicates the amount of lecithin present in the naphtha inthe form of the reaction product. As shown by the table, the ability ofFe Xto increase octane is better than iron tetracarbonyl but not as goodas iron pentacarbonyl. However, the reaction product has the advantagebeing fairly stable in the presence of light and air; whereas ironpentacarbonyl rapidly deteriorates unless lecithin is present, and evenin the case of lecithin it is not as stable It has previously beenpointed out that the reaction takes place only between polymeric metalcarbonyls and phosphatides. An attempt to react iron pentacarbonyl, amonomeric carbonyl, with lecithin produced no color change in as the FeX reaction product. the solutipn when heated and stirred under the Thenovel knock inhibitor composition in acconditions hereinbefore set forthfor the reaccordance with my invention may be prepared in tion betweenlecithin and iron tetracarbonyl. concentrated solution in a solvent suchas The color of the reaction product between naphtha or toluene and theconcentrated solum lecithin and iron tetracarbonyl varies from dark tionused as the knock inhibitor additive or-the yellow through brown to darkred, depending phosphatide and carbonyl may be added in the upon theconcentration of the solution in which desired amounts to thegasolinewhose knock it is prepared. The -more dilute solutions are r t g it isdesired to improve and the mixture yellow and the most concentratedsolutions are he d to the desired temperature. e y. red. It a smallamount of a concentrated solu- 1 1'70-180 F., to form the reaction pro uin tion of the reaction product is added to motor situ. In preparing thedesired reaction product fuel or naphtha the color of the naphtha at thetemperature should be sufliciently high to first tum red but uponstanding from 24 to 72 caufse g; rgpld fi gz ggg i s ig g g gf hours thecolor changes to dark yellow or brown, to 6 0mm on p depending on theamount of concentrate. ucts. At temperatures below F.- reaction In orderto dete the stabmt of various takes place very slowly, whereas attemperatures 1 t1 1 m minim d t y 1 above 240 F. decomposition productsform with u ms 0 e react on Pro uc a number 0 appreciable amounts ofprecipitate. At atmossamples were Prepared with varying of pherictemperatures of E no visible 25 iron tetracarbonyl to lecithin and thesamples action appears to take place. At temperatures were Permitted tostand in glass bottles in ilo1 -l80 F. reaction is completed in from 15li ht at atmospheric temperatures w all to 20 minutes without anynoticeable decompoin the top 01! the bottles. The results oi. thesition. storage tests are given in Table II:

Table II Extent 0:! preci ltate forma- Fewo) Solvent or fuel Color afterays sample Mol. phosphstide on used 10 days Trace Slight Appreclsbloalteraiter-- aiter (Heat. 1 0.28 Petroleum naph- Yellow 3i 1 the. 2 L40.76 do Deepyellow 31 1 3 E 1.25 .do Amber.- 15 31 1 4 3.00 do Darkbrown10 31 l 1 b tl i ll 1 l6#l,000bbls. A be s1 2 3322312 iiiflbtil5333133812381 Ewhow 1.1.1.3.. D ap mben 15 31 c-1 11.4 do Darkbrown 1 221 1 C 1 1 0.76 Gasoline .1 21

1 09.9 Pettgolsum naph- Deep red 36 l 21 B. C 2 .1 0.5 Gasoline YellowI14 1 z 2 E9 1.0 .do Darkyellow 1 C 2. 3 2.0 .do Amber 6 l4 1 c .g Z1)4.0 .do Brown 2 14 1 z 5 0.5 Ethyl gasollne Lightred 14 1 c. 3 L13 67.2Toluene Deepreduu 14 1 C 3 1 E 0.5 Gasoline Yellow I14 1 C32 1.0 .(10Darkyellow 14 1 g 2.0 -do Amber e 14 1 0-34.-- 1-2 4.0 .do Brown 2 14 i1 0-3-5... 5* 0.5 -.---do .r Lightred 14 1 (3-4 fl 113.6 Toluene Deepred 11 1 C44 4.0 Gasoline Brown 10 1 C5 113.6 Toluene Deepred 2 5 10 10-5-4- 4.0 Gasoline Brown 1 10 In the foregoing table samples 1-8 werepre-' pared by forming the reaction product in situ in"the naphtha.Samples C-l, 2, 0-3, 0-4 {and C4 represent concentrated solutions of thereaction product which were prepared and the remaining samples wereprepared by blending these concentrated solutions of the reactionproduct with motor fuel. It is apparent from the results in the tablethat the most stable solutions are prepared by forming the reactionproducts in situ in motor fuel in proportions in which it is desired touse them and that the smaller the amount of reaction product insolution, the. more stable is the resulting solution. It is furtherapparent that the most stable concentrate' that was prepared was theconcentrate prepared using toluene as the solvent. Aromatic hydrocarbonsolvents are therefore preferred because of their stabilizing effect onthe reaction product. The addition of isobutyl p-aminophenol had noeffect on the stability of the solutions but did affect the colorthereof, causing them to become considerably darker.

The reaction products formed by the reaction of the polymeric metalcarbonyls and the phosphatides can be reduced to'the solid form byevaporating concentrates thereof either at room temperature or by gentleheating. The solid product is clear, dark brown in color, is nonstickyand non-brittle, is stable in air indefinitely andresembles a soft resinor plastic. This product can be redissolved in gasoline or aromaticsolvents to give the required motor fuel blend or concentrate.

The stabilization of motor fuel containing metal carbonyls by additionof phosphatides to the fuel is claimed in my co-pending applicationSerial No. 415,065.

I' claim:

1. Amotor fuel comprising a major portion of hydrocarbons boiling withingasoline boiling range and a minor portion of the reaction productobtained by reacting a phosphatide with a polymeric metal carbonylwithin the temperature range of approximately 150-240 F. in the absenceof oxygen.

2. A motor fuel in accordance with claim 1 in which the phosphatide islecithin. a

3. A motor fuel in accordance with claim 1 in which the phosphatide iscephalin.

4. A motor fuel in accordance with claim 1 in which the polymeric metalcarbonyl is iron tetracarbonyl.

5. A motor fuel in accordance with claim 1 in which the polymeric metalcarbonyl is cobalt tetracarbonyl. v

6. A motor fuel in accordance with claim 1 in which the polymeric metalcarbonyl is cobalt tricarbonyl.

7. A motor fuel comprising a major portion of hydrocarbons boilingwithin gasoline boiling range and a minor portion of the reactionproduct obtained by reacting between approximately 1 to 10 moles ofpolymeric metal carbonyl with approximately 1 mol of a phosphatide at atemperature between approximately 150-240 F. in the absence of oxygen.

8. A composition of matter useful as amadditive for motor fuelscomprising the reaction product of a polymeric metal carbonyl and aphosphatide at a temperature between approximately 150 and 240 F. in theabsence of oxygen.

9. A composition in, accordance with claim 8 12. Method of preparing amotor fuel additive 0 comprising reacting a polymeric metal carbonylwith a phosphatide at a temperature between approximately 150 and 240 F.in the absence of oxygen.

13. Method in accordance with claim 12 in which the proportion in molesof polymeric metal carbonyl to phosphatide ranges from approximately 10to 1 of the former to 1 part of the latter.

14. Method in accordance with claim 12 in which the phosphatide islecithin.

15. Method in accordance with claim 12 in which-the metal carbonyl is apolymeric iron being present in the form of anoxygen-free solution in aninert solvent.

18. A motor fuel additive comprising the reaction product obtained byheating a polymeric iron carbonyl and a solution of a phosphatide in aninert aromatic solvent to a temperature of approximately -180" F. in theabsence of oxygen until the reaction is completed, the molar ratioof'carbonyl to phosphatide being from 1 to 0 10 of the former to 1 ofthe latter- RICHMIOND T. BEIL.

